Patent GB-688757-A (GB)
Title: Quaternary nitrogen compounds and process of producing same
IPC: C07D213/20
Filed: 1949-06-03
Abstract: Benzene is condensed with a C9-C18 propylene polymer, the product halomethylated to give an alkyl-substituted benzyl halide and the latter reacted with a tertiary base to form a quaternary ammonium halide; the tertiary base contains at the most 12 carbon atoms with no more than 7 in any one substituent; cyclic bases such as pyridine, alkylpyridines, N-methylpiperidine and N-methylmorpholine are included.  The polypropylene (mixture) preferably boils at 300-600 DEG  F. (especially tetramers and pentamers boiling at 360-520 DEG F.), obtained by phosphoric acid polymerization of propylene, and has a greater optical density at p  10.35 m  than at 11.23 m , i.e. consists mainly of R-CH=CH-R1 rather than RR1C=CH2.  On reacting such a polypropylene (mixture) with benzene using hydrofluoric acid or other catalyst, the main mono-alkyl-benzene fraction boils at 475-650 DEG  F., which is then chloromethylated or bromomethylated.  The product is mainly alkyl substituted benzyl halide with some substituted xylylene dihalide, and is then reacted with the tertiary base with or without separation. Compounds prepared in the examples are: polypropylenes, dodecylbenzene, dodecylbenzyl chloride, dodecylbenzyl - pyridinium chloride, dodecylbenzyl-triethylammonium chloride, dodecylbenzyl-benzyl-dimethylammonium chloride, and dodecylbenzyl-b -hydroxyethyl - diethyl - ammonium chloride.  The tertiary base may be a trialkylamine, a trialkanolamine, a benzyl-dialkylamine or a tertiary cycloalkylamine (e.g. cyclohexyl-dimethylamine) besides the heterocyclic bases mentioned above.  The Specification as open to inspection under Sect. 91 refers to quaternary salts in general of the formula Alkyl-aryl-CH2-NBX, where the alkyl group is of 8-18 carbon atoms (preferably branched-chain), the aryl nucleus may be that of toluene or naphthalene as well as benzene, NB is the residue of a tertiary base defined as above and X is an anion which may be (in addition to chloride or bromide) iodide, nitrate, sulphate, phosphate, carbonate, nitrite, alkyl-sulphate, alkyl - phosphate, formate, acetate, lactate, citrate or tartrate.  The alkyl group may be derived from (1) fats or fatty oils by catalytic hydrogenation; (2) petroleum hydrocarbons by chlorination or cracking; or (3) Fischer-Tropsch olefines.  The group may be introduced into the nucleus by condensing the aromatic hydrocarbon with the appropriate olefine, alcohol or halide.  Specified alkyl radicals are 2-octyl, 2-decyl, 2-dodecyl, 2-hexadecyl, iso-octyl, isononyl, isodecyl and isopentadecyl. When using cracked petroleum fractions, those olefines which split up under the conditions of condensation with the aromatic hydrocarbon are first removed, e.g. by selective adsorption on silica gel, silica, alumina or charcoal.  Details are given of the separation procedure.  When using Fischer-Tropsch olefines, separation of oxygen-containing impurities is necessary to get a quaternary salt free from odour.  Aldehydes, ketones and acids are removed with hot caustic solutions or sodium bisulphite.  Alcohols may be extracted by selective solvents (e.g. methanol), azeotropic distillation (e.g. with butylene glycol) or esterification with boric acid. Alternatively, the Fischer-Tropsch olefines may be purified by adsorption on charcoal or silica gel, when oxygenated compounds and aromatic hydrocarbons are removed.  In further examples: (1) dodecene-1 is reacted with benzene and the product chloromethylated and condensed with triethylamine; (2) benzene is treated with tetradecene-1 to give 2-phenyltetradecane which is chloromethylated and reacted with pyridine; (3) benzene is similarly converted to 2-phenyldecane, chloromethylated and reacted with pyridine; (4) octadecyl-benzyl ammonium chloride is reacted with triethanolamine; (5) thermally-cracked naphtha (B.P. 350-500 DEG  F.) is purified with silica gel and reacted with benzene in the presence of hydrogen fluoride; the product is chloro-methylated and condensed with pyridine, triethylamine or benzyldimethylamine; (6) a suitable Fischer-Tropsch fraction is purified with silica gel, condensed with benzene, the product chloromethylated and reacted with pyridine, triethylamine or benzyldimethylamine; (7) a petroleum fraction (B.P. 342-405 DEG  F.) is chlorinated and condensed with benzene in the presence of aluminium chloride; the product is chloromethylated and reacted with pyridine, triethylamine or benzyldimethylamine; (8) isobutane is reacted with isobutene and hydrogen fluoride to give a fraction boiling at 360-408 DEG  F.; this is chlorinated and further treated as in (7).  There are also mentioned substituted benzylpyridinium chlorides derived from 2-phenyloctane and 2-phenyl-2-chlorododecane.  This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specifications 659,353 and 666,892.ALSO:Wetting agents comprise quaternary ammonium halides obtained by reacting tertiary bases with halomethylated alkylbenzenes where the alkyl group is derived from a propylene polymer (mixture) consisting of R-CH=CH-R1 rather than RR1C=CH2. Specified compounds are dodecylbenzyl-pyridinium chloride, dodecylbenzyl - triethylammonium chloride, dodecylbenzyl - benzyl - dimethylammonium chloride, and dodecylbenzyl - b  - hydroxyethyl - diethyl - ammonium chloride.  The tertiary base used may be a trialkylamine, trialkanolamine, a benzyldialkylamine, a tertiary cycloalkylamine or a heterocyclic base.  Other specified bases are cyclohexyl-dimethylamine, alkylpyridines, N-methylpiperidine and N-methyl-morpholine.  The base contains at the most 12 carbon atoms, with no more than 7 in any one substituent.  The Specification as open to inspection under Sect. 91 refers to quaternary salts in general of the formula Alkyl-aryl-CH2-NBX, where the alkyl group is of 8-18 carbon atoms (preferably branched-chain), the aryl nucleus may be that of toluene or naphthalene as well as benzene, NB is the residue of a tertiary base defined as above and X is an anion which may be (in addition to chloride or bromide) iodide, nitrate, sulphate, phosphate, carbonate, nitrite, alkyl - sulphate, alkyl - phosphate, formate, acetate, lactate, citrate or tartrate.  The alkyl group may be derived from (1) fats or fatty oils by catalytic hydrogenation; (2) petroleum hydrocarbons by p  chlorination or cracking; or (3) Fischer-Tropsch olefines. Specified alkyl radicals are 2-octyl, 2-decyl, 2-dodecyl, 2-hexadecyl, iso-octyl, isononyl, isodecyl and isopentadecyl. Additional compounds mentioned are tetradecylbenzyl-pyridinium chloride, decylbenzyl - pyridinium chloride, octylbenzyl - pyridinium chloride, chlorodecylbenzyl - pyridinium chloride, octadecylbenzyl-tri-(b -hydroxyethyl)-ammonium chloride and the alkylbenzylpyridinium chlorides, alkylbenzyl - triethylammonium chlorides and alkylbenzyl-benzyldimethylammonium chlorides where the alkyl group is derived from (1) thermally-cracked naphtha olefines, (2) Fischer-Tropsch olefines, (3) chlorinated paraffin, and (4) isobutane-isobutene condensates.  This subject-matter does not appear in the Specification as accepted.  Reference has been directed by the Comptroller to Specifications 659,353 and 666,892, [both in Group IV (b)].ALSO:Germicidal compositions contain as their active ingredient a quaternary ammonium halide obtained by reacting a tertiary base with a halomethylated alkylbenzene where the alkyl group is derived from a propylene polymer (mixture) consisting of R-CH = CH-R1 rather than RR1C = CH2.  Specified compounds are dodecylbenzyl-pyridinium chloride, dodecylbenzyl-triethyl-ammonium chloride, dodecylbenzylbenzyl-dimethylammonium chloride and dodecylbenzyl-b -hydroxyethyl-diethylammonium chloride.  The tertiary base used may be a trialkylamine, a trialkanolamine, a benzyldialkylamine, a tertiary cycloalkylamine or a heterocyclic base.  Other specified bases are cyclohexyl-dimethylamine, alkylpyridines, N-methylpiperidine and N-methylmorpholine.  The base contains at the most 12 carbon atoms, with no more than 7 in any one substituent. The quaternary halides may be used in aqueous or alcoholic solution, if desired with stabilising or solubilising agents such as isopropyl alcohol, glycol, glycol ethers and polyglycols and auxiliary detergents, preferably of the non-ionic type.  The quaternary halides are themselves wetting agents and may be used as solubilisers or dispersants for other medicants, e.g., cresols.  The Specification as open to inspection under Sect. 91, refers to quaternary salts in general of the formula Alkyl-aryl-CH2-NBX where the alkyl group is of 8-18 carbon atoms (preferably branched-chain), the aryl nucleus may be that of toluene or naphthalene as well as benzene, NB is the residue of a tertiary base defined as above and X is an anion which may be (in addition to chloride or bromide) iodide, nitrate, sulphate, phosphate, carbonate, nitrite, alkyl-sulphate, alkyl-phosphate, formate, acetate, lactate, citrate or tartrate.  The alkyl group may be derived from (1) fats or fatty oils by catalytic hydrogenation, (2) petroleum hydrocarbons by chlorination or cracking or (3) Fischer-Tropsch olefines.  Specified alkyl radicals are 2-octyl, 2-decyl, 2-dodecyl, 2-hexadecyl, isooctyl, isononyl, isodecyl and isopentadecyl.  Additional compounds mentioned are tetradecylbenzyl-pyridinium chloride, decylbenzyl-pyridinium chloride, octylbenzyl pyridinium chloride, chlorododecylbenzyl pyridinium chloride, octadecylbenzyl-tri-(B1-hydroxyethyl)-ammonium chloride and the alkylbenzyl-pyridinium chlorides, alkylbenzyl-triethylammonium chlorides and alkylbenzyl-benzyl-dimethylammonium chlorides where the alkyl group is derived from (1) thermally-cracked naphtha olefines, (2) Fischer-Tropsch olefines, (3) chlorinated paraffin and (4) isobutane-isobutene condensates.  This subject-matter does not appear in the Specifications as